CN111333122B - Mixed conductor, lithium-air battery, and method for producing a mixed conductor - Google Patents

Mixed conductor, lithium-air battery, and method for producing a mixed conductor Download PDF

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CN111333122B
CN111333122B CN201911171441.7A CN201911171441A CN111333122B CN 111333122 B CN111333122 B CN 111333122B CN 201911171441 A CN201911171441 A CN 201911171441A CN 111333122 B CN111333122 B CN 111333122B
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equal
ltoreq
less
air battery
lithium
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CN111333122A (en
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李铉杓
权赫载
马祥福
徐东和
林东民
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Samsung Electronics Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention relates to a hybrid conductor, a lithium-air battery, and a method of preparing a hybrid conductor. A mixed conductor represented by the formula 1, wherein in the formula 1, A is at least one element of group 1 of the periodic table of elements, M is at least one metal element of groups 2 to 16 of the periodic table of elements, provided that M is neither Ti nor Mn, and 0.ltoreq.x is satisfied<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1. 1A 1±x M 2±y O 4‑δ 。

Description

Mixed conductor, lithium-air battery, and method for producing a mixed conductor
Cross Reference to Related Applications
This application claims priority and equity of korean patent application No.10-2018-0164307 filed in the korean intellectual property office on 12 months of 2018, and ownership equity generated therefrom, the contents of which are incorporated herein by reference in their entirety.
Technical Field
The present disclosure relates to a hybrid conductor, an electrochemical device including the same, and a method of preparing the hybrid conductor.
Background
In an electrochemical device such as a battery, an electrochemical reaction occurs when ions and electrons move between a plurality of electrodes along separate movement paths and then combine at the electrodes.
An ion conductor for transporting ions and an electron conductor for transporting electrons are mixed and arranged in the electrode.
In the electrode, for example, an organic liquid electrolyte is used as an ion conductor, and a carbon-based conductive agent is used as an electron conductor. The organic liquid electrolyte and the carbon-based conductive agent are easily decomposed by radicals generated through an electrochemical reaction, thereby deteriorating the performance of the battery. In the electrode, the carbon-based conductive agent suppresses diffusion/transfer of ions, and the organic liquid electrolyte suppresses transfer of electrons, so that the internal resistance in the battery increases.
Thus, there remains a need for conductors that are chemically stable to byproducts of electrochemical reactions and that can transfer ions and electrons simultaneously.
Disclosure of Invention
A mixed conductor is provided that is chemically stable and simultaneously transfers ions and electrons.
An electrochemical device including the mixed conductor is provided.
Methods of making the hybrid conductor, positive electrode, and lithium air battery are provided.
Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the presented embodiments.
According to an aspect of one embodiment, there is provided a hybrid conductor represented by formula 1.
1 (1)
A 1±x M 2±y O 4-δ
Wherein in formula 1, A is at least one element of group 1 of the periodic Table of elements, M is at least one metal element of groups 2 to 16 of the periodic Table of elements, provided that M is neither Ti nor Mn, and 0.ltoreq.x <1, 0.ltoreq.y.ltoreq.1 and 0.ltoreq.delta.ltoreq.1 are satisfied.
According to an aspect of another embodiment, a lithium air battery includes: a positive electrode including the mixed conductor; a negative electrode including lithium metal; and an electrolyte between the positive electrode and the negative electrode.
According to an aspect of another embodiment, a method of preparing a hybrid conductor includes: providing an element a precursor; mixing an element a precursor and an element M precursor to prepare a mixture; and heat-treating the mixture in a solid phase to produce a mixed conductor; wherein A is at least one element of group 1 of the periodic Table of the elements, and M is at least one metal element of groups 2 to 16 of the periodic Table of the elements, with the proviso that M is neither Ti nor Mn.
Also disclosed is a method of manufacturing a positive electrode, the method comprising: providing a hybrid conductor; a redox catalyst, a binder and a solvent that provide oxygen; mixing the mixed conductor, an oxygen redox catalyst, a binder, and a solvent to obtain a positive electrode material; and disposing the positive electrode material on a surface of a substrate to manufacture a positive electrode.
Also disclosed is a method of manufacturing a lithium air battery, the method comprising: disposing an electrolyte layer on a negative electrode including lithium; and disposing a positive electrode including the mixed conductor on the electrolyte layer to manufacture a lithium air battery.
Drawings
These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments taken in conjunction with the accompanying drawings, wherein:
fig. 1 is a schematic diagram illustrating a transition (transition) process (transition process) of Li in the spinel crystal structure of a mixed conductor according to an embodiment of the present disclosure;
fig. 2 is a graph showing the intensities (arbitrary units, a.u) of the results of X-ray diffraction analysis (XRD) of examples 1 to 3 with respect to the diffraction angles (degrees, 2θ); and
fig. 3 is a schematic view illustrating the structure of a lithium air battery according to an embodiment of the present disclosure.
Detailed Description
Reference will now be made in detail to the embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as limited to the descriptions set forth herein. Accordingly, the embodiments are described below to explain aspects by referring to the figures only. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. When a expression such as "at least one of" precedes or follows a list of elements, the entire list of elements is modified and the individual elements of the list are not modified.
The present disclosure described below is susceptible to various modifications and alternative forms, examples of which are therefore shown in the accompanying drawings and will be described in detail with reference to the drawings. However, it should be understood that the exemplary embodiments of the concepts according to the present disclosure are not limited to the embodiments described below with reference to the drawings, but that various modifications, equivalents, additions and substitutions are possible, without departing from the scope and spirit of the present disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, "a," "an," "the," and "at least one" do not denote a limitation of quantity, and are intended to include both the singular and the plural, unless the context clearly indicates otherwise. For example, unless the context clearly indicates otherwise, "an element (element)" has the same meaning as "at least one element (element)". It will be further understood that the terms "comprises," "comprising," "includes," "including" and/or "having," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. As used herein, the term "/" may be interpreted as "and" or "depending on the circumstances, including any and all combinations of one or more of the associated listed items. "or" means "and/or".
In the drawings, diameters, lengths and thicknesses are exaggerated or reduced to clearly illustrate various components, layers and regions. Throughout the specification, like reference numerals refer to like elements (components). It will be understood that when a layer, film, region, sheet, etc. is referred to throughout this specification as being "on" another portion, this includes not only the case directly on the other portion, but also the case where there are other portions therebetween. Although the terms first, second, etc. may be used herein to describe various elements (components), these elements (components) should not be limited by these terms. These terms are only used to distinguish one element from another element.
As used herein, "about" or "approximately" includes the stated values and means within an acceptable deviation of the particular values as determined by one of ordinary skill in the art in view of the measurement in question and the error associated with the measurement of the particular quantity (i.e., limitations of the measurement system). For example, "about" may mean within one or more standard deviations of the stated values, or within ±30%, 20%, 10% or 5%.
Unless defined otherwise, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Exemplary embodiments are described herein with reference to cross-sectional illustrations that are schematic illustrations of idealized embodiments. In this way, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, the embodiments described herein should not be construed as limited to the particular shapes of regions illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, the regions shown or described as being flat may typically have rough and/or nonlinear features. Furthermore, the sharp corners shown may be rounded. Accordingly, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the claims.
As used herein, "mixed conductor" refers to a conductor that provides both ionic conductivity and electronic conductivity. For example, with Li 4 Ti 5 O 12 The hybrid conductors used herein provide improved ionic and electronic conductivity at the same time as those of the other.
The electron conductivity can be measured by an eddy current method or a Kelvin bridge method. Electronic conductivity can be measured according to ASTM B-193, "Standard Test Method for Resistivity of Electrical Conductor Materials", e.g., at 20 ℃, or according to ASTM E-1004, "Standard Test Method for Determining Electrical Conductivity Using the Electromagnetic (Eddy-Current) Method", e.g., at 20 ℃. Additional details can be determined by one of ordinary skill in the art without undue experimentation.
The ionic conductivity can be determined by the complex impedance method at 20℃and for further details see J.—M.Wiand et al, "Measurement of Ionic Conductivity in Solid Electrolytes", europhysics Letters, vol.8, no.5, pages 447-452, 1989.
Hereinafter, a hybrid conductor, an electrochemical device including the same, and a method of preparing the hybrid conductor according to example embodiments will be described in more detail.
The hybrid conductor according to the embodiment is represented by formula 1.
1 (1)
A 1±x M 2±y O 4-δ
Wherein in formula 1, A is at least one element of group 1 of the periodic Table of elements, M is at least one metal element of groups 2 to 16 of the periodic Table of elements, provided that M is neither Ti nor Mn, and 0.ltoreq.x <1, 0.ltoreq.y.ltoreq.1 and 0.ltoreq.delta.ltoreq.1 are satisfied. Delta may indicate oxygen vacancy content.
The mixed conductor has the above composition, wherein a is at least one group 1 element of the periodic table of elements, M is at least one metal element of groups 2 to 16 of the periodic table of elements, and M is at least one metal other than Ti and Mn, thereby improving both ionic conductivity and electronic conductivity. Furthermore, the mixed conductor as an inorganic oxide is stable to heat and chemically stable to radicals accompanying the electrochemical reaction.
A may comprise at least one alkali metal of Li, na, K, rb or Cs. For example, a may include at least one alkali metal of Li, na, or K. For example, a may be Li.
M may be at least one metal element of the following: mg, ca, sr, fe, ru, co, ni, pd, ag, pt, cu, zn, cd, hg, ge, sn, pb, po, sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, cr, rh, au, al, ga, in, tl, sb, bi, zr, hf, mo, re, ir, V, nb, ta or Tc.
For example, M may be at least one metal element of the following: co, ni, fe, V, zr, cu, zn, mo, ru, nb, ta, pd or Ag. In one aspect, M comprises at least one of Ni, V, nb, or Ta. Embodiments are mentioned wherein M is at least one of Ni and Nb.
In one aspect, 0.ltoreq.x <0.5,0< x <0.4 or 0.1< x <0.2; y < 0< 1,0< y <0.8 or 0.1< y <0.4; and 0.ltoreq.delta.1, 0.ltoreq.delta.0.5 or 0.1.ltoreq.delta.ltoreq.0.5.
The above formula 1 may be represented by formula 2.
2, 2
A 1±x' M' 2-z' M” z' O 4-δ'
In formula 2, A is an element of group 1 of the periodic Table of the elements, M ' and M ' are each independently at least one metal element of groups 2 to 16 of the periodic Table of the elements, provided that M ' or M ' is neither Ti nor Mn, and 0.ltoreq.x ' <1, 0.ltoreq.z '. Ltoreq.1, and 0.ltoreq.delta '. Ltoreq.1 are satisfied. Delta' may indicate oxygen vacancy content. In one aspect, 0.ltoreq.x ' <0.5,0< x ' <0.4, or 0.1< x ' <0.2;0<z '. Ltoreq.1, 0< z ' <0.8 or 0.1< z ' <0.4; and 0.ltoreq.delta ' <1, 0.ltoreq.delta ' <0.5 or 0.1.ltoreq.delta '. Ltoreq.0.5.
M 'and M' are metallic elements and are different from each other. For example, M' and m″ are metal elements having oxidation numbers different from each other or having the same oxidation number as each other. When metal elements having different oxidation numbers from each other are mixed, and not wishing to be bound by theory, it is understood that a hybrid orbit formed by mixing molecular orbitals of M' and m″ increases a new density function of states, and thus the band gap between the valence and conduction bands decreases. As a result, the electron conductivity of the mixed conductor is improved.
According to an embodiment, M' and m″ may be metal elements having oxidation numbers different from each other. For example, the oxidation number of the M 'metal element may be less than the oxidation number of the M' metal element. For example, the metal element m″ may be a pentavalent cation.
Formula 1 may be represented by formula 3 or 4:
3
Li 1±x M 2±y O 4-δ Or (b)
4. The method is to
Li 1±x' M' 2-z' M” z' O 4-δ'
In formulas 3 and 4, M, M' and m″ are each independently at least one metal element of the following: mg, ca, sr, fe, ru, co, ni, pd, ag, pt, cu, zn, cd, hg, ge, sn, pb, po, sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, cr, rh, au, al, ga, in, tl, sb, bi, zr, hf, mo, re, ir, V, nb, ta or Tc, 0.ltoreq.x <1, 0.ltoreq.y.ltoreq.1, 0.ltoreq.delta.ltoreq.1, 0.ltoreq.x ' <1, 0.ltoreq.z '.ltoreq.1 and 0.ltoreq.delta '. Ltoreq.1. Delta and delta' may indicate oxygen vacancy content.
For example, M and M' may be Mg, ca, sr, fe, ru, co, ni, pd, ag, pt, cu, zn, cd, hg, ge, sn, pb, po, sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, cr, rh, au, al, ga, in, tl, sb, bi, zr, hf, mo, re or Ir, and M "may be V, nb, ta, or Tc.
For example, M and M' may be Co, ni, fe, zr, cu, zn, mo, ru, pd or Ag, and M "may be V, nb or Ta. Mention is made of aspects in which M and M' are Ni and M "is Nb.
In one aspect, 0.ltoreq.x <0.5,0< x <0.4 or 0.1< x <0.2; 0.ltoreq.z <1,0< z <0.8 or 0.1< z <0.4; and 0.ltoreq.delta.1, 0.ltoreq.delta.0.5 or 0.1.ltoreq.delta.ltoreq.0.5. Further, in one aspect, 0.ltoreq.x ' <0.5,0< x ' <0.4, or 0.1< x ' <0.2;0<z '. Ltoreq.1, 0< z ' <0.8 or 0.1< z ' <0.4; and 0.ltoreq.delta ' <1, 0.ltoreq.delta ' <0.5 or 0.1.ltoreq.delta '. Ltoreq.0.5.
The hybrid conductor may include, but is not limited to, at least one of the following: li (Li) 1±x Co 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; li (Li) 1±x Ni 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; li (Li) 1±x Fe 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; li (Li) 1±x Zr 2±y O 4-δ Wherein 0.ltoreq.x<1, y is more than or equal to 0 and less than or equal to 1 and 0 is more than or equal to 0δ≤1；Li 1±x Cu 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; li (Li) 1±x Zn 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; li (Li) 1±x Mo 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; li (Li) 1±x Ru 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; li (Li) 1±x Pd 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; and Li (lithium) 1±x Ag 2±y O 4-δ Wherein 0.ltoreq.x<Y is more than or equal to 1 and less than or equal to 0 and less than or equal to 1, and delta is more than or equal to 0 and less than or equal to 1; li (Li) 1±x' Co 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Ni 2-z' V z' O 4-δ Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Fe 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Zr 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Cu 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Zn 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Mo 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Ru 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Pd 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; and Li (lithium) 1±x' Ag 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Co 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Ni 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Fe 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Zr 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Cu 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Zn 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Mo 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Ru 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Pd 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; and Li (lithium) 1±x' Ag 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; and Li (lithium) 1±x' Co 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Ni 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Fe 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Zr 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Cu 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Zn 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Mo 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Ru 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; li (Li) 1±x' Pd 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1; or Li (lithium) 1±x' Ag 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.2x'<1，0<z 'is less than or equal to 1 and 0 is less than or equal to delta' is less than or equal to 1. Any suitable mixed conductor represented by formulas 1 to 4 above may be used.
The mixed conductor may include a phase having a spinel crystal structure. For example, the mixed conductor may be formed to have a spinel crystal structure. Because the mixed conductor has a spinel crystal structure, it can be electrochemically stable.
The spinel crystal structure may include Fd3m space groups. For example, the spinel crystal structure may include a cubic spinel crystal structure.
When analyzed by XRD using Cu Ka radiation, the mixed conductor may have peaks at diffraction angles of 36.0±2.5° 2θ and 43.0±2.5° 2θ. Furthermore, the mixed conductor can maintain the same crystal structure even if some of the transition metal is replaced with a different type of transition metal.
The mixed conductor has a suitable electron conductivity and a suitable ionic conductivity. For example, the mixed conductor has both a higher Li than Li having a spinel structure 4 Ti 5 O 12 Ion conductivity and electron conductivity of (a) are high.
The mixed conductor has a thickness of about 4.5x10 -9 Siemens/centimeter (S/cm) or higher. For example, the hybrid conductor may have a thickness of about 5x10 -9 S/cm or higher, about 1x10 -8 S/cm or higher, about 1x10 -7 S/cm or higher, about 1x10 -6 S/cm or higher, about 1x10 -5 S/cm or higher, or about 1x10 -4 S/cm or higher. For example, the hybrid conductor may have a thickness of about 4.5x10 -9 S/cm to about 1x10 -3 S/cm, about 5X10 -9 S/cm to about 5x10 -4 S/cm, about 1X10 -8 S/cm to about 8x10 -4 S/cm, about 1X10 -7 S/cm to about 1x10 -5 S/cm, about 1X10 -6 S/cm to about 2x10 -5 S/cm, about 1X10 -5 S/cm to about 3x10 -4 S/cm, or about 1x10 -4 S/cm to about 2x10 -2 S/cm electron conductivity. When the mixed conductor has such electron conductivity, the internal resistance of the electrochemical device including the mixed conductor decreases.
The mixed conductor has a thickness of about 7x10 -8 S/cm or higher. For example, the hybrid conductor may have a thickness of about 8x10 -8 S/cm or higher, about 9x10 -8 S/cm or higher, about 1x10 -7 S/cm or higher, or about 1x10 -6 S/cm or higher. For example, the hybrid conductor may have a thickness of about 7x10 -8 S/cm to about 1x10 -4 S/cm, about 8x10 -8 S/cm to about 5x10 -4 S/cm, about 9X10 -8 S/cm to about 1x10 -5 S/cm, about 1X10 -7 S/cm to about 8x10 -6 S/cm, or about 1x10 -6 S/cm to 9x10 -6 S/cm ionic conductivity. The mixed conductor has such an ionic conductivity that the internal resistance of an electrochemical device including the mixed conductor is reduced.
The band gap between the valence and conduction bands of the mixed conductor is smaller than Li 4 Ti 5 O 12 Is a band gap of (c). For example, the band gap of the mixed conductor between the valence and conduction bands is about 2.5 electron volts (eV) or less, about 2.3eV or less, about 2.0eV or less, about 1.8eV or less, about 1.6eV or less, about 1.4eV or less, or about 1.2eV or less. For example, the band gap of the mixed conductor between the valence and conduction bands is about 2.5eV to about 1.2eV, about 2.3eV to about 1.4eV, about 2.0eV to about 1.6eV, about 1.8eV to about 1.4eV, about 1.6eV to about 1.2eV, about 1.6eV to about 1eV. When the band gap of the mixed conductor between the valence band and the conduction band has such a low value, movement of electrons from the valence band to the conduction band is promoted, so that the electron conductivity of the mixed conductor is improved.
The mixed conductor may include oxygen vacancies. While not wishing to be bound by theory, it is understood that oxygen vacancies provide improved ionic conductivity. For example, when the mixed conductor includes oxygen vacancies, the position of the state density function moves around the fermi energy (Ef), and thus the band gap between the valence and conduction bands decreases. As a result, the electron conductivity of the mixed conductor is further improved.
In the mixed conductor, for example, referring to fig. 1, a is located on at least one of the tetrahedral 8a site and the octahedral 16c site of the spinel crystal structure. Referring to FIG. 1, when A is lithium, it is used to transfer lithium from one tetrahedral 8a site viaThe activation energy of lithium transition from the octahedral 16c site to the other tetrahedral 8a site (Ea, 8a->16c->8a) Less than Li 4 Ti 5 O 12 Is used for lithium transition from one tetrahedral 8a site to another tetrahedral 8a site via the octahedral 16c site (Ea, 8a->16c->8a) A. The invention relates to a method for producing a fibre-reinforced plastic composite When the mixed conductor has a value less than Li 4 Ti 5 O 12 Is used for lithium transition from one tetrahedral 8a site to another tetrahedral 8a site via the octahedral 16c site (Ea, 8a->16c->8a) The transfer and/or diffusion of lithium ions in the mixed conductor becomes easier. As a result, with Li 4 Ti 5 O 12 The ionic conductivity of the mixed conductor is increased compared to that of the mixed conductor.
An electrochemical device according to another embodiment may include the above-described mixed conductor. When the electrochemical device includes the mixed conductor that is chemically stable and simultaneously transfers ions and electrons, degradation of the electrochemical device is suppressed.
Examples of electrochemical devices may include, but are not limited to, batteries, accumulators, supercapacitors, fuel cells, sensors, and electrochromic devices. Any suitable electrochemical device may be used as long as it can be used in the art.
The battery may be, for example, a primary battery or a secondary battery. Examples of batteries may include, but are not limited to, lithium batteries and sodium batteries. Any suitable battery may be used as long as it can be used in the art. Examples of lithium batteries may include, but are not limited to, lithium ion batteries and lithium air batteries. Any suitable lithium battery may be used as long as it can be used in the art. Examples of electrochromic devices may include, but are not limited to, electrochemical mirrors, electrochemical windows, electrochemical screens, and electrochemical facades (surfaces). Any suitable electrochromic device may be used as long as it can be used in the art.
The electrochemical device comprising the mixed conductor may be, for example, a lithium air battery.
The lithium air battery may include a positive electrode. The positive electrode may be an air electrode. The positive electrode may be disposed on, for example, a positive electrode current collector.
The positive electrode may include the above-described mixed conductor. In this case, the positive electrode is configured to use oxygen as a positive electrode active material. The mixed conductor may act as a reaction site for oxygen and lithium ions transferred from the anode and electrolyte during discharge, and discharge products may be deposited on the surface of the mixed conductor. The mixed conductor may serve as a channel for transporting lithium ions and electrons and may not directly participate in oxidation and/or reduction reactions upon discharge or charge of the lithium-air battery.
The positive electrode may further include a conductive material. The conductive material may be porous, for example. The porosity of the conductive material promotes air permeation. Any suitable conductive material may be used as long as it has suitable porosity and/or conductivity and is available in the art. For example, the conductive material may be a carbon-based material having suitable porosity. Examples of carbon-based materials may include, but are not limited to, carbon black, graphite, graphene, activated carbon, or carbon fibers. Any suitable carbon-based material may be used. The conductive material may be, for example, a metallic material. Examples of metallic materials include metallic fibers, metallic mesh, or metallic powder. Examples of the metal powder include copper powder, silver powder, or aluminum powder. The conductive material may be, for example, an organic conductive material. Examples of the organic conductive material include a polyphenylene derivative or a polythiophene derivative. The conductive materials may be used alone or as a mixture thereof. The positive electrode may include the mixed conductor as a conductive material, and the positive electrode may include the above-described conductive material in addition to the mixed conductor.
The positive electrode may further include a catalyst for oxidation and/or reduction of oxygen. Examples of catalysts may include, but are not limited to, metal catalysts including metals such as platinum, gold, silver, palladium, ruthenium, rhodium, or osmium; oxide catalysts, such as manganese oxide, iron oxide, cobalt oxide or nickel oxide; organometallic catalysts such as cobalt phthalocyanine. Any suitable catalyst may be used as long as it can be used in the art.
The catalyst may be supported on, for example, a carrier. Examples of the carrier may include an oxide carrier, a zeolite carrier, a clay-based mineral carrier, and a carbon carrier. The oxide support may be, for example, a metal oxide support, and may include at least one metal or semi-metal of the following: al, si, zr, ti, ce, pr, sm, eu, tb, tm, yb, sb, bi, V, cr, mn, fe, co, ni, cu, nb, mo or W. The oxide support may comprise, for example, alumina, silica, zirconia or titania. Examples of the carbon support may include, but are not limited to, carbon black such as ketjen black, acetylene black, channel black, or lamp black; graphite such as natural graphite, artificial graphite or expanded graphite; activated carbon; or carbon fiber. Any suitable carrier may be used.
The positive electrode may further include, for example, a binder. The binder may include, for example, a thermoplastic resin or a thermosetting resin. Examples of the binder may include, but are not limited to, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-pentafluoropropene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, or ethylene-acrylic acid copolymer, which may be used alone or in a mixture thereof. Any suitable adhesive may be used.
The positive electrode can be prepared by, for example, the following: mixing a conductive material, an oxygen redox catalyst, and a binder to obtain a mixture, adding an appropriate solvent to the mixture to obtain a positive electrode slurry, and then applying the positive electrode slurry onto a surface of a substrate and drying the applied positive electrode slurry, or compression molding the positive electrode slurry onto the substrate. The substrate may be, for example, a positive electrode current collector, a separator, or a solid electrolyte membrane. The positive electrode current collector may be, for example, a gas diffusion layer. The conductive material may include the mixed conductor, and in the positive electrode, the oxidation-reduction catalyst and the binder of oxygen may be omitted according to the kind of the desired positive electrode.
The lithium air battery includes a negative electrode. The negative electrode may include lithium.
The negative electrode may be, for example, a lithium metal film or a lithium-based alloy film. The lithium-based alloy may be, for example, an alloy of lithium and aluminum, tin, magnesium, indium, calcium, titanium, or vanadium.
The lithium-air battery may include an electrolyte layer between the positive electrode and the negative electrode.
The electrolyte layer may include at least one of a solid electrolyte, a gel electrolyte, or a liquid electrolyte. The solid electrolyte, the gel electrolyte, and the liquid electrolyte are not limited, and any suitable electrolyte may be used.
The solid electrolyte may include, but is not limited to, at least one of the following: a solid electrolyte comprising an ion conducting inorganic material, a solid electrolyte comprising a polymeric ionic liquid and a lithium salt, or a solid electrolyte comprising an ion conducting polymer and a lithium salt. Any suitable solid electrolyte may be used.
The ion conducting inorganic material may include, but is not limited to, at least one of the following: a glassy or amorphous metal ion conductor, a ceramic active metal ion conductor, or a glassy ceramic active metal ion conductor. Any suitable ion conducting inorganic material may be used. The ion conducting inorganic material may be made in the form of ion conducting inorganic particles or sheets thereof.
For example, the ion conducting inorganic material may include at least one of: baTiO 3 Pb (Zr) wherein 0.ltoreq.a.ltoreq.1 a Ti 1-a )O 3 (PZT), where 0.ltoreq.x<1、0≤y<Pb of 1 1-x La x Zr 1-y Ti y O 3 (PLZT)，Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT)，HfO 2 ，SrTiO 3 ，SnO 2 ，CeO 2 ，Na 2 O，MgO，NiO，CaO，BaO，ZnO，ZrO 2 ，Y 2 O 3 ，Al 2 O 3 ，TiO 2 ，SiO 2 SiC, lithium phosphate (Li) 3 PO 4 ) Lithium titanium phosphate (Li) x Ti y (PO 4 ) 3 Wherein 0 is<x<2，0<y<3) Lithium aluminum titanium phosphate (Li) x Al y Ti z (PO 4 ) 3 Wherein 0 is<x<2，0<y<1 and 0<z<3) Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 1, and b is more than or equal to 0 and less than or equal to Li which is less than or equal to 0 and less than or equal to 1 1+x+y (Al a Ga 1-a ) x (Ti b Ge 1-b ) 2-x Si y P 3-y O 12 Lithium lanthanum titanate (Li) x La y TiO 3 Wherein 0 is<x<2，0<y<3) Lithium germanium thiophosphate (Li) x Ge y P z S w Wherein 0 is<x<4，0<y<1，0<z<1 and 0<w<5) Lithium nitride (Li x N y Wherein 0 is<x<4，0<y<2) SiS-based 2 Glass (Li) x Si y S z Wherein 0 is<x<3,0<y<2 and 0<z<4 based on P 2 S 5 Glass (Li) x P y S z Wherein 0 is<x<3，0<y<3 and 0<z<7)，Li 2 O，LiF，LiOH，Li 2 CO 3 ，LiAlO 2 Based on Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TiO 2 -GeO 2 Or garnet-based ceramics (Li 3+x La 3 M 2 O 12 Wherein 0.ltoreq.x.ltoreq.4 and M=Te, nb, zr), or combinations thereof.
The polymeric ionic liquid may include repeating units that may include: i) At least one of the following cations: ammonium cation, pyrrolidinium cation, pyridinium cation, pyrimidinium cation, imidazolium cation, piperidinium cation, pyrazolium cation,An azolium cation, a pyridazinium cation, a phosphonium cation, a sulfonium cation, a triazolium cation, or mixtures thereof, and ii) at least one of the following: BF (BF) 4 - 、PF 6 - 、AsF 6 - 、SbF 6 - 、AlCl 4 - 、HSO 4 - 、ClO 4 - 、CH 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、Cl - 、Br - 、I - 、SO 4 2- 、CF 3 SO 3 - 、(C 2 F 5 SO 2 )(CF 3 SO 2 )N - 、NO 3 - 、Al 2 Cl 7 - 、CF 3 COO - 、CH 3 COO - 、(CF 3 SO 2 ) 3 C - 、(CF 3 CF 2 SO 2 ) 2 N - 、(CF 3 ) 2 PF 4 - 、(CF 3 ) 3 PF 3 - 、(CF 3 ) 4 PF 2 - 、(CF 3 ) 5 PF - 、(CF 3 ) 6 P - 、SF 5 CF 2 SO 3 - 、SF 5 CHFCF 2 SO 3 - 、CF 3 CF 2 (CF 3 ) 2 CO - 、(CF 3 SO 2 ) 2 CH - 、(SF 5 ) 3 C - Or (O (CF) 3 ) 2 C 2 (CF 3 ) 2 O) 2 PO - . Examples of polymeric ionic liquids may include poly (bis (trifluoromethanesulfonyl) imide diallyldimethylammonium), poly (bis (trifluoromethanesulfonyl) imide 1-allyl-3-methylimidazolium), and poly (bis (trifluoromethanesulfonyl) imide N-methyl-N-propylpiperidinium).
The ion conducting polymer may include at least one ion conducting repeat unit derived from an ether-based monomer, an acrylic monomer, a methacrylic monomer, or a siloxane-based monomer.
Examples of ion conducting polymers may include, but are not limited to, polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyvinylsulfone, polypropylene oxide (PPO), polymethyl methacrylate, polyethyl methacrylate, polydimethylsiloxane, polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polyethyl acrylate, 2-ethylhexyl acrylate, polybutyl methacrylate, 2-ethylhexyl methacrylate, decyl polyacrylate, polyethylene vinyl acetate, phosphate polymers, polyester sulfides, polyvinylidene fluoride (PVdF), or lithium substituted NAFION (Li-NAFION). Any suitable ion conducting polymer may be used.
Examples of electron conducting polymers may include, but are not limited to, polyphenylene derivatives and polythiophene derivatives. Any suitable electron conducting polymer may be used.
The gel electrolyte may be obtained by adding a low molecular solvent to a solid electrolyte between the anode and the cathode. The gel electrolyte may be obtained by adding a solvent, an oligomer, or the like (which may be a low molecular organic compound) to the polymer. The gel electrolyte may be obtained by adding a solvent, an oligomer, or the like (which may be a low molecular organic compound) to the above polymer electrolyte.
The liquid electrolyte may include a solvent and a lithium salt.
The solvent may include, but is not limited to, at least one of an organic solvent, an ionic liquid, or an oligomer. Any suitable solvent may be used as long as it can be liquid at room temperature (25 ℃) and can be used in the art.
The organic solvent may include at least one of an ether-based solvent, a carbonate-based solvent, an ester-based solvent, or a ketone-based solvent. Examples of the organic solvent may include, but are not limited to, propylene carbonate, ethylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylisopropyl carbonate, dipropyl carbonate, dibutyl carbonate, benzonitrile, acetonitrile, gamma-butyrolactone, dioxolane, 4-methyldioxolane, dimethylacetamide, dimethylsulfoxide, di-n-ethyl carbonate, and the like Alkane, 1, 2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, succinonitrile, diglyme (deggme), tetraglyme (teggme), polyethylene glycol dimethyl ether (PEGDME, mn= -500), dimethyl ether, diethyl ether, dibutyl ether, dimethoxyethane, 2-methyltetrahydrofuranA furan or tetrahydrofuran. Any suitable organic solvent may be used as long as it is liquid at room temperature (25 ℃).
The Ionic Liquid (IL) may comprise i) at least one of the following cations: ammonium cation, pyrrolidinium cation, pyridinium cation, pyrimidinium cation, imidazolium cation, piperidinium cation, pyrazolium cation,An azolium cation, a pyridazinium cation, a phosphonium cation, a sulfonium cation, a triazolium cation, or mixtures thereof, and ii) at least one of the following anions: BF (BF) 4 - 、PF 6 - 、AsF 6 - 、SbF 6 - 、AlCl 4 - 、HSO 4 - 、ClO 4 - 、CH 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、Cl - 、Br - 、I - 、SO 4 2 -、CF 3 SO 3 - 、(C 2 F 5 SO 2 )(CF 3 SO 2 )N - 、NO 3 - 、Al 2 Cl 7 - 、CF 3 COO - 、CH 3 COO - 、(CF 3 SO 2 ) 3 C - 、(CF 3 CF 2 SO 2 ) 2 N - 、(CF 3 ) 2 PF 4 - 、(CF 3 ) 3 PF 3 - 、(CF 3 ) 4 PF 2 - 、(CF 3 ) 5 PF - 、(CF 3 ) 6 P - 、SF 5 CF 2 SO 3 - 、SF 5 CHFCF 2 SO 3 - 、CF 3 CF 2 (CF 3 ) 2 CO - 、(CF 3 SO 2 ) 2 CH - 、(SF 5 ) 3 C - Or (O (CF) 3 ) 2 C 2 (CF 3 ) 2 O) 2 PO - 。
The lithium salt may include, but is not limited to, at least one of the following: liTFSI (LiN (SO) 2 CF 3 ) 2 )、LiPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 、LiNO 3 Lithium bis (oxalato) borate (LiBOB), liN (SO) 2 C 2 F 5 ) 2 、LiC(SO 2 CF 3 ) 3 、LiN(SO 3 CF 3 ) 2 、LiC 4 F 9 SO 3 、LiAlCl 4 Or LiTfO (lithium triflate, liCF) 3 SO 3 ). Any suitable lithium salt may be used as long as it can be used in the art. The concentration of lithium salt may be, for example, about 0.01 mole/L (M) to 5.0M.
The lithium air battery may further include a separator between the positive electrode and the negative electrode. The separator is not limited as long as it can withstand the potential range of the lithium air battery. For example, the separator may include a polymer nonwoven such as a nonwoven made of polypropylene or a nonwoven made of polyphenylene sulfide, a porous film made of polyolefin such as polyethylene or polypropylene, or glass fibers, and may include a combination of two or more thereof.
The electrolyte layer may have, for example, a structure in which the separator is impregnated with a solid polymer electrolyte or a structure in which the separator is impregnated with a liquid electrolyte. The electrolyte layer having a structure in which the separator is impregnated with the solid polymer electrolyte may be prepared by, for example, the following: the solid polymer electrolyte membrane is applied to one or both sides of the separator, and then the solid polymer electrolyte membrane and the separator are simultaneously rolled. The electrolyte layer having a structure in which the separator is impregnated with the liquid electrolyte may be prepared by, for example, injecting the liquid electrolyte containing a lithium salt into the separator.
The lithium air battery can be completed by the following steps: a negative electrode is disposed at one side surface in the case, an electrolyte layer is disposed on the negative electrode, a positive electrode is disposed on the electrolyte layer, a porous positive electrode current collector is disposed on the positive electrode, a pressing member is disposed on the porous positive electrode current collector to transfer air to the air electrode, and the pressing member is pushed to fix the unit cell. The case may be divided into an upper portion contacting the negative electrode and a lower portion contacting the air electrode, and an insulating resin is interposed between the upper portion and the lower portion to electrically insulate the positive electrode from the negative electrode.
Lithium air batteries can be used for both primary and secondary batteries. The shape of the lithium air battery is not limited, and examples thereof include coins, buttons, sheets, laminates, cylinders, plates, and cones. The lithium air battery may also be suitable for medium-and large-sized batteries of electric vehicles.
Fig. 3 schematically illustrates the structure of a lithium air battery according to an embodiment. The lithium-air battery 500 includes a positive electrode 200 adjacent to the first current collector 210 and configured to use oxygen as an active material, a negative electrode 300 adjacent to the second current collector 310 and including lithium, and a first electrolyte layer 400 interposed between the positive electrode 200 and the negative electrode 300. The first electrolyte layer 400 is a separator impregnated with a liquid electrolyte. The second electrolyte layer 450 is disposed between the positive electrode 200 and the first electrolyte layer 400. The second electrolyte layer 450 is a solid electrolyte membrane having lithium ion conductivity. The first current collector 210 may also function as a gas diffusion layer that is porous and capable of diffusing air. The pressing member 220 is disposed on the first current collector 210 to transfer air to the positive electrode. A case 320 made of an insulating resin material is interposed between the positive electrode 200 and the negative electrode 300 to electrically isolate the positive electrode 200 and the negative electrode 300. Air is supplied into the air inlet 230a and discharged to the outside through the air outlet 230 b. The lithium air battery may be housed in a stainless steel container.
As used herein, the term "air" is not limited to atmospheric air and may include combinations of gases comprising oxygen or pure oxygen. The broad definition of the term "air" is applicable to all applications, such as air cells, air electrodes, and the like.
The method of preparing a hybrid conductor according to an embodiment may include: mixing an element a precursor and an element M precursor to prepare a mixture; and heat-treating the mixture in a solid phase to produce a mixed conductor.
The preparation of the mixture may further comprise mixing an element M' precursor and an element M "precursor, which are different from each other.
The preparation of the mixture may be carried out by ball milling the precursor of element a, the precursor of element M, and if desired the precursor of element M' and the precursor of element M "in an organic solvent and/or an aqueous solution. The organic solvent may be an alcohol such as 2-propanol or ethanol, but is not limited thereto. Any suitable organic solvent may be used. The process of reacting the mixture in a solid phase may mean that the reaction is carried out by heat treatment in the absence of a solvent.
The mixed conductor to be prepared is described above with reference.
The precursor of element A may be a salt of A, an oxide of A, a hydroxide of A or a carbonate of A, the precursor of element M may be a salt of M, an oxide of M, a hydroxide of M or a carbonate of M, the precursor of element M ' may be a salt of M ', an oxide of M ', a hydroxide of M ' or a carbonate of M ', and the precursor of element M "may be a salt of M", an oxide of M ", a hydroxide of M" or a carbonate of M ".
The elemental a precursor may be, for example, a lithium precursor. Examples of lithium precursors may include, but are not limited to, li 2 CO 3 、LiNO 3 、LiNO 2 、LiOH、LiOH.H 2 O、LiH、LiF、LiCl、LiBr、LiI、CH 3 OOLi、Li 2 O、Li 2 SO 4 Lithium carboxylates, lithium citrates, lithium fatty acids and lithium alkyls. Any suitable lithium precursor may be used as long as it can be used in the art. For example, the lithium precursor may be LiOH or Li 2 CO 3 。
The elemental M precursor may include at least one of the following: alkoxides, chlorides, oxides, hydroxides, nitrates, carbonates or acetates each including at least one metal element of group 2 to 16 elements other than Ti or Mn, but are not limited thereto. For example, the elemental M precursor may be NiO 2 。
The element M' precursor may include at least one of: the alkoxide, chloride, oxide, hydroxide, nitrate, carbonate, or acetate may each include at least one metal element of group 2 to 16 elements other than Ti or Mn, but is not limited thereto. Any suitable precursor of element M' may be used as long as it can be used in the art. For example, the precursor of element M' may be NiO 2 。
The element M "precursor may include at least one of the following: alkoxides, chlorides, oxides, hydroxides, nitrates, carbonates, or acetates, and each may include at least one metal element of V, nb, ta, or Tc, but is not limited thereto. Any suitable precursor of element M "may be used as long as it can be used in the art. For example, the precursor of element M "may be Nb 3 O 5 。
In the method of preparing a mixed conductor, preparing a mixed conductor by reacting a mixture in a solid phase may include: drying the mixture and subjecting the dried mixture to a first heat treatment in an oxidizing atmosphere to produce a first heat treated product; crushing and pressing the first heat-treated product to prepare a pellet; and subjecting the sheet to a second heat treatment in a reducing atmosphere, an oxidizing atmosphere, or both an oxidizing atmosphere and a reducing atmosphere.
In the second heat treatment, a reducing atmosphere, an oxidizing atmosphere, or both of an oxidizing atmosphere and a reducing atmosphere may be selected depending on the oxidation number of the metal contained in the target mixed conductor.
The reducing atmosphere may be an atmosphere comprising a reducing gas. The reducing gas may be, for example, hydrogen (H) 2 ) But is not limited thereto. Any suitable reducing gas may be used. The reducing atmosphere may be a mixture of a reducing gas and an inert gas. The inert gas may be, for example, nitrogen or argon, but is not limited thereto. Any suitable inert gas may be used. The amount of reducing gas in the reducing atmosphere may be, for example, from about 1 volume percent (vol%) to about 99 vol%, from about 2 vol% to about 50 vol%, or from about 5 vol% to about 20 vol%, based on the total volume of the reducing atmosphere. The heat treatment may be performed under a reducing atmosphere, and oxygen vacancies may be introduced into the mixed conductor by the heat treatment performed under a reducing atmosphere.
The oxidizing atmosphere may be an atmosphere comprising an oxidizing gas. The oxidizing gas may be, for example, oxygen or air, but is not limited thereto. Any suitable oxidizing gas may be used as long as it can be used in the art. The oxidizing atmosphere may be a mixture of an oxidizing gas and an inert gas. The inert gas may be the same as the inert gas used in the reducing atmosphere.
The second heat treatment in the oxidizing atmosphere and the reducing atmosphere refers to a second heat treatment in which heat treatment in the oxidizing atmosphere and heat treatment in the reducing atmosphere may be sequentially performed. The oxidizing atmosphere and the reducing atmosphere may be the same as the foregoing oxidizing atmosphere and the foregoing reducing atmosphere.
The first heat treatment may be performed, for example, at about 600 ℃ to about 1,000 ℃, about 700 ℃ to about 900 ℃, or about 750 ℃ to about 850 ℃. The first heat treatment time may be from about 2 hours to about 10 hours, from about 3 hours to about 9 hours, from about 4 hours to about 8 hours, or from about 4 hours to about 6 hours. The second heat treatment may be performed, for example, at about 700 ℃ to about 1,400 ℃, about 800 ℃ to about 1,300 ℃, about 900 ℃ to about 1,200 ℃, or about 900 ℃ to about 1,100 ℃. The second heat treatment time may be from about 6 hours to about 48 hours, from about 10 hours to about 40 hours, from about 15 hours to about 35 hours, or from about 20 hours to about 30 hours. The first heat treatment and the second heat treatment may be performed under these conditions, thus further improving the electrochemical stability of the prepared mixed conductor.
Hereinafter, the present disclosure will be described in more detail with reference to examples and comparative examples. However, these embodiments are set forth to illustrate the present disclosure, and the scope of the present disclosure is not limited thereto.
Examples
Preparation of mixed conductors
Example 1 (LiNi) 2 O 4 )
Lithium precursor Li 2 CO 3 And nickel precursor Ni (OH) 2 Mixed with each other in a stoichiometric ratio, mixed with ethanol, and then pulverized and mixed at 280rpm for 4 hours using a planetary ball mill including zirconia balls to obtain a mixture. The obtained mixture was dried at 90℃for 6 hours, and then subjected to a heat treatment at 650℃for 5 hours in an air atmosphere. The primary heat-treated mixture was pulverized for 4 hours using a ball mill, and then the mixture was dried for a second time at 90 ℃ for 6 hours. The twice dried mixture was pressed under isostatic pressure to obtain tablets. The obtained tablet was subjected to an air atmosphere at 9A secondary heat treatment was performed at 50 ℃ for 24 hours to prepare a mixed conductor. The composition of the prepared mixed conductor is LiNi 2 O 4 。
Example 2 (LiNi) 1.9 Nb 0.1 O 4 )
Lithium precursor Li 2 CO 3 Ni (OH) nickel precursor 2 And niobium precursor Nb 2 O 5 Mixed with each other in a stoichiometric ratio, mixed with ethanol, and then pulverized and mixed for 4 hours at 280rpm by using a planetary ball mill including zirconia balls to obtain a mixture. The obtained mixture was dried at 90℃for 6 hours, and then subjected to a heat treatment at 650℃for 5 hours in an air atmosphere. The primary heat-treated mixture was pulverized for 4 hours using a ball mill, and then the mixture was dried for a second time at 90 ℃ for 6 hours. The twice dried mixture was pressed under isostatic pressure to obtain tablets. The obtained sheet was subjected to a secondary heat treatment at 950 ℃ for 24 hours in an air atmosphere to prepare a mixed conductor. The composition of the prepared mixed conductor is LiNi 1.9 Nb 0.1 O 4 。
Example 3 (LiNi) 1.8 Nb 0.2 O 4 )
Lithium precursor Li 2 CO 3 Ni (OH) nickel precursor 2 And niobium precursor Nb 2 O 5 Mixed with each other in a stoichiometric ratio, followed by addition of ethanol, and then pulverized and mixed at 280rpm by using a planetary ball mill including zirconia balls for 4 hours to obtain a mixture. The obtained mixture was dried at 90℃for 6 hours, and then subjected to a heat treatment at 650℃for 5 hours in an air atmosphere. The primary heat-treated mixture was pulverized for 4 hours using a ball mill, and then the mixture was dried for a second time at 90 ℃ for 6 hours. The twice dried mixture was pressed under isostatic pressure to obtain tablets. The obtained sheet was subjected to a secondary heat treatment at 950 ℃ for 24 hours in an air atmosphere to prepare a mixed conductor. The composition of the prepared mixed conductor is LiNi 1.8 Nb 0.2 O 4 。
Comparative example 1 (Li) 4 Ti 5 O 12 )
Under isostatic pressure in the same manner as in example 1Compacting commercially available Li 4 Ti 5 O 12 Powder to prepare tablets.
Evaluation example 1: evaluation of electronic conductivity
Gold (Au) was sputtered on both sides of each of the mixed conductor sheets prepared in examples 1 to 3 and comparative example 1 to complete an ion-blocking battery (cell) (ion blocking cell). The electron conductivity was measured using DC polarization.
The time-dependent current obtained when a constant voltage of 100 millivolts (mV) was applied for 30 minutes on the completed symmetric cell was measured. The electronic resistance of the mixed conductor is calculated from the measured current, and the electronic conductivity of the mixed conductor is calculated from the calculated electronic resistance. The calculated electronic conductivities are given in table 1 below.
Evaluation example 2: evaluation of ion conductivity
Separator layers impregnated with a liquid electrolyte (1M LiTFSI in Propylene Carbonate (PC)) were disposed on both sides of each of the mixed conductor sheets prepared in examples 1-3 and comparative example 1, and a stainless steel current collector was disposed on the separator layers to complete an electron blocking battery. The ionic conductivity was measured using DC polarization.
The time-dependent current obtained when a constant voltage of 100mV was applied to the completed symmetrical cell for 30 minutes was measured. After calculating the resistance of the battery from the measured current, the ionic resistance of the separator layer is subtracted from the ionic resistance of the battery to calculate the ionic resistance of the hybrid conductor, and the ionic conductivity is calculated from the calculated ionic resistance. The calculated ionic conductivities are given in table 1 below.
TABLE 1
Composition of the composition Electronic conductivity (S/cm) Ion conductivity (S/cm)
Comparative example 1 Li 4 Ti 5 O 12 4.3x 10 -9 6.8x 10 -8
Example 1 LiNi 2 O 4 1.66x 10 -3 1.63x 10 -4
Example 2 LiNi 1.9 Nb 0.1 O 4 4.72x 10 -5 3.67x 10 -7
Example 3 LiNi 1.8 Nb 0.2 O 4 2.42x 10 -5 2.2x 10 -6
As shown in table 1 above, the mixed conductors prepared in examples 1 to 3 were improved in both electron conductivity and ion conductivity as compared to the electron conductivity and ion conductivity of the conductor of comparative example 1.
Evaluation example 3: evaluation of XRD
The crystals of the mixed conductors of examples 1 to 3 were analyzed by X-ray powder diffraction (XRD). The results are shown in fig. 2.
Referring to FIG. 2, due to the LiNi of example 1 2 O 4 And the mixed conductors of examples 2 and 3 in which a portion of Ni was replaced with Nb ions exhibited the same XRD pattern, it was found that in the examples with Nb substitution, nb substitution was at the site of Ni without collapse or change in the crystal structure.
According to the embodiment, when a mixed conductor that is chemically stable and simultaneously transfers ions and electrons is used, deterioration of the electrochemical device is suppressed.
It should be understood that the embodiments described herein should be considered in descriptive sense only and not for purposes of limitation. The description of features or aspects in each embodiment should be considered as applicable to other similar features or aspects in the disclosed embodiments.
Although embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.

Claims (20)

1. A lithium air battery comprising:
a positive electrode including a mixed conductor represented by formula 1;
a negative electrode including lithium metal; and
an electrolyte between the positive electrode and the negative electrode:
1 (1)
A 1±x M 2±y O 4-δ
Wherein, in the formula 1,
a is Li, and is represented by the formula,
M is at least one of the following: ni, V, nb, ta, or Pd
Wherein in formula 1, x <0.2, y <0.4 and delta < 0.5 are satisfied,
wherein the positive electrode is configured to use oxygen as a positive electrode active material.
2. The lithium air battery of claim 1, wherein M is at least one of: ni, V, nb or Ta.
3. The lithium air battery according to claim 1, wherein in formula 1, x=0, 0.ltoreq.y <0.4, and 0.ltoreq.δ.ltoreq.0.5.
4. The lithium air battery according to claim 1, wherein 0.ltoreq.x <0.2, y=0, and 0.ltoreq.δ.ltoreq.0.5 in formula 1.
5. The lithium air battery according to claim 1, wherein 0.ltoreq.x <0.2, 0.ltoreq.y <0.4, and δ=0 in formula 1.
6. The lithium air battery of claim 1, wherein formula 1 is represented by formula 2:
2, 2
A 1±x' M' 2-z' M” z' O 4-δ'
Wherein, in the formula 2,
a is Li, and is represented by the formula,
m 'and M' are each independently at least one of: ni, V, nb, ta, or Pd
Wherein in formula 2, 0.ltoreq.x ' <0.2, 0.ltoreq.z '. Ltoreq.1 and 0.ltoreq.delta '. Ltoreq.0.5 are satisfied.
7. The lithium air battery of claim 6, wherein M' and M "have different oxidation numbers from each other.
8. The lithium air battery of claim 6, wherein the oxidation number of the M' metal element is less than the oxidation number of the M "metal element.
9. The lithium air battery of claim 6, wherein M' is Ni and M "is at least one of V, nb or Ta.
10. The lithium air battery according to claim 6, wherein in formula 2, x ' =0, 0< z ' +.1, and 0+.delta ' +.0.5 are satisfied.
11. The lithium air battery of claim 1, wherein the hybrid conductor comprises: li (Li) 1±x Ni 2±y O 4-δ Wherein 0.ltoreq.x<0.2，0≤y<0.4 and 0.ltoreq.delta.ltoreq.0.5; li (Li) 1±x Pd 2±y O 4-δ Wherein 0.ltoreq.x<0.2，0≤y<0.4 and 0.ltoreq.delta.ltoreq.0.5; li (Li) 1±x' Ni 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<0.2，0<z 'is less than or equal to 1, and delta' is less than or equal to 0 and less than or equal to 0.5; li (Li) 1±x' Pd 2-z' V z' O 4-δ' Wherein 0.ltoreq.x'<0.2，0<z 'is less than or equal to 1, and delta' is less than or equal to 0 and less than or equal to 0.5; li (Li) 1±x' Ni 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<0.2，0<z 'is less than or equal to 1, and delta' is less than or equal to 0 and less than or equal to 0.5; li (Li) 1±x' Pd 2-z' Nb z' O 4-δ' Wherein 0.ltoreq.x'<0.2，0<z 'is less than or equal to 1, and delta' is less than or equal to 0 and less than or equal to 0.5; li (Li) 1±x' Ni 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<0.2，0<z 'is less than or equal to 1, and delta' is less than or equal to 0 and less than or equal to 0.5; li (Li) 1±x' Pd 2-z' Ta z' O 4-δ' Wherein 0.ltoreq.x'<0.2，0<z 'is less than or equal to 1, and delta' is less than or equal to 0 and less than or equal to 0.5; or a combination thereof.
12. The lithium air battery of claim 1, wherein the mixed conductor comprises a phase having a spinel crystal structure.
13. The lithium air battery of claim 12, wherein the spinel crystal structure has Fd3m space groups.
14. The lithium air battery of claim 1, wherein the hybrid conductor has a peak at a diffraction angle of 36.0±2.5°2Θ and a peak at a diffraction angle of 43.0±2.5°2Θ when analyzed by X-ray powder diffraction using Cu ka radiation.
15. The lithium air battery of claim 1, wherein the hybrid conductor has a length of 4.5 x 10 -9 Siemens/cm to 2 x 10 -3 Siemens/cm electron conductivity.
16. The lithium air battery of claim 1, wherein the hybrid conductor has a 7 x 10 -8 Siemens/cm to 2 x 10 -4 Ion conductivity of siemens/cm.
17. The lithium air battery of claim 1, wherein the mixed conductor has a band gap between the valence and conduction bands that is less than Li 4 Ti 5 O 12 Is a band gap of (c).
18. The lithium air battery of claim 1, wherein the mixed conductor has a band gap between the valence and conduction bands of 2.5 electron volts to 1.2 electron volts.
19. The lithium air battery of claim 1, wherein when a is lithium, the activation energy for lithium transition from one tetrahedral 8a site to another tetrahedral 8a site via the octahedral 16c site is less than Li 4 Ti 5 O 12 Is used for lithium transition from one tetrahedral 8a site to another tetrahedral 8a site via the octahedral 16c site.
20. The lithium air battery of claim 1, wherein the electrolyte comprises a solid electrolyte.
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